Process for breaking petroleum emulsions



Patented June 17, 1947 UNITED STATES PATENT OFFICE PROCESS FOR BREAKINGPETROLEUM EMULSIQNS No Drawing. Application December .10, 1943 SerialNo. 513,784

Claims. 1

This invention relates primarily to the treatment of emulsions ofmineral .oil and water, such as petroleum emulsions, for the purpose ofseparating the oil from the water. It is a continuation-in-part of mypending application for patent Serial N 0. 462,887, filed October 1,1.942.

One object of my present invention is to provide a novel process forresolving petroleum emulsions of the water-in-oil type, that arecommonly referred to as cut oil, "roily oil, and "emulsified oil," etc.,and which comprises fine droplets of naturally-occurring waters ofbrines dispersed in a more or less permanent state throughout the oilwhich constitutes the continuous phase of the emulsion.

Another object of my invention is to provide an economical and rapidprocess for separating emulsions which have been prepared undercontrolled conditions from mineral oil, such as crude petroleum, andrelatively soft waters or weak brines. Controlled 'emulsification andsubsequent demulsification, under the conditions just mentioned, is ofsignificant value in removing impuri ties, particularly inorganic saltsfrom pipeline oil.

The new composition of matter herein described, which constitutes thedemulsifying agent of my improved process for resolving petroleumemulsions. constitutes a class of high molecular weight esters and esteracids together with their salts.

Reference is hereby directed to my aforementioned pending applicationfor patent Serial No. 462,887, filed October 1, 1942. In saidapplication it was pointed .out that the condensation product of analpha/beta ethylenic acid, or anhydride with an unsaturated,non-conjugated, nonhydroxylated fatty acid or fatty acid ester,constitutes a class of products having utility for breaking petroleumemulsions. In said application it was also pointed out that variousderivatives of these condensation products are efiective demulsifiers,and among such derivatives was mentioned the esters prepared by reactingthe acidic condensation product with tertiary alkanolamines.

I have found that if one introduces a certain functional group or groupsinto the chemical compound or condensation product of an alphabetaethylenic acid or anhydride with an unsaturated, non-conjugated,non-hydroxylated fatty acid, one obtains .a sub-genus or speciedescribed in the above-mentioned pending application, which is decidedlyeffective for use as a .demulsifier. as well as offering similarefiectiveness for other purposes. In the present instance the inventionis concerned with the sub-genus 01 species which contains a tertiarybasic amim group in :the form of an ester. Such .iunctiona .group .orradical appears to co operate in :som 5 non-obvious manner with theremainder of thq molecule to yield a product which is unusuall:effective as a demulsifying agent. Such type although disclosed in myaforementioned co pending application, is not specifically claimeztherein.

Briefly stated, such compounds are obtaine; by esterification of theadduct with basic tertiar: alkanolamines containing at least one hydroxygroup, such as triet'hanolamine. "The amine ma: contain alkyl or alkanolradicals, in which th carbon chains may interrupted by oxygen, 0:arylalkyl groups, in which the aryl radical is no linked directly to thenitrogen atom. Example of suitable tertiary alkanolamines includetriethanolamine, butyldiethanolamine, diethylpro panolamine,benzyldiethanolamine, cetyldietha nolamine, cyclohexylethylethanolamine,and tin like.

Such reactions of the kind just indicated, t wit, esterification, mayresult in a residual hy droxyl radical if the alkanolamine contains morthan one hydroxyl group. As is hereinafter in dicated, such hydroxylradical may be esterifiel with various polycarboxy acids, as described,0 with monocarboxy acids having 8 carbon atom or less, such as octanoic,hexanoic, acetic, hy dxoxyacetic, lactic acid, etc. The acidic .condensation product or adduct with which thes tertiary alkanolamines arereacted has bee] completely described in the above mentione'application, but to make the present applicatioi complete within itself,these products will b described in detail.

As mentioned previously, these condensatio: products are themselvespolybasic acids or anhy drides. -It has recently been disclosed in U. .5Patents Nos. 2,188,882 to 2,188,890, inclusive dated January 30, 1940,to Clocker, and in 01' and Soap" by Bickford, et 8.1., in the Februar;1942 issue at pages 23 et seq., that these product may be obtained byheating the reactants at suitably elevated temperature, usually above200 C., and sometimes at temperatures above 300 C The alpha-betaethylenic acids or anhydride which are suitable for use in thisaiorementione condensation with non-conjugated, unsaturatednon-hydroxylated fatty acids, are those contain ing less than 10 carbonatoms, and are exempli 65 fled by .crotonic acid, maieic acid, fumaricacid Actually, as pointed out by Clocker in the above mentioned patents,the esters of these acids, such as the triglycerides or the esters ofmonoor dior other polyhydric alcohols, may be employed in thiscondensation, in place of the fatty acid itself. Esters of sorbitol,mannitol, sorbitan, mannitan, 'etc., may be used. For the production ofdemulsifiers contemplated by my process, I usually prefer to employ acondensation product derived from a glyceride containing in esterifiedform, a large proportion of non-conjugated, unsaturated,non-.hydroxylated, fatty acid. Erramples of such glycerides are oliveoil, corn oil, cottonseed oil, soyabean oil, linseed oil, rapeseed oil,Perilla oil, cranberryseed oil, teaseed oil, etc.

When glycerides or other esters of the .nonconjugated, unsaturated,non-hydroxylated fatty acids are employed in the condensation reaction,the final product is not necessarily a. polybasic bid or anhydride,since a monocarboxy, alphabeta ethylenic acid, such as crotonic acid,may have been employed in the condensation. However, such monobasic acidcondensation products are intended to be included when reference is madeto a polybasic carboxy acid or anhydride reactant used in preparingthedemulsifiers contemplated by my present invention. Actually, they arethe partial esters of dibasic acids, and under certain conditions, mayfunction as polybasic acids by interchange of the alcohol residue with ahydroxyl-containing reactant. This aspect is clarified by contemplatingthe final product as derived from a polybasic carboxy acid, in

which one carboxy radical is part of an unsatu-.-

rated, non-conjugated, higher fatty acid, as described. The othercarboxy radicalor radicals are derived from the alpha-beta ethylenicacid.

For the sake of convenience and clarity, the

. reactants which are derived as described above by condensation of analpha-beta ethylenic carboxy acid with a non-conjugated, unsaturated,non-hydroxylated, fatty acid or fatty acid ester, will be referred tobelow as Clocker adducts. Previous reference has been made to the factthat the functional group which characterizes the herein contemplatedsub-genus or species, contains a tertiary basic aminoalkanol group, inwhich the alkyl or alkanol chains contain from 2 to 20 carbon atoms,triethanolamine being the most readily available source of such agrouping. The carbon atom chain may be interrupted by oxygen atoms.

The manufacture of typical Clocker adducts are illustrated by thefollowing examples:

Acrnrc CLOCKER AnnUcr Example A 880 lbs. of linseed oil was heated with295 lbs. of maleic anhydride while stirring under an air condenser. Thetemperature was raised to 250 C. and held for 2 hours. Constantagitation was employed during the course of reaction. The progress ofthe reaction was noted by determination of the maleic anhydride number,i. e., the

extent to which the maleic anhydride or its equivalent has disappearedby the formation of an adduct. See Berichte der Deutcher ChemisheGesellschaft, vol. 70, part B, page 903, et seq. (1937), and Analyst,vol. 61, page 812 (1936). If the reaction is incomplete at the end of 2hours, as indicated by any suitable analytical procedure, one continuesheating and agitating until the reaction is complete, or substantiallycomplete.

AcInIc CLOCKER AnnUc'r Example B 880 lbs. of soyabean oil was heatedwith 196 lbs. of maleic anhydride while stirring under an air condenser.The temperature was held at 250 C. for 2 hours.

, Acrnrc CLOCKER Annncr Example C 'I'easeed (olive) oil was substitutedfor the soyabean oil in Example B.

' 224 lbs. of citraconic anhydride was substituted for the 196 lbs. ofmaleic anhydride in Exam ple B.

Acrnrc Crocxsa Annucr Example F 300 lbs. of Indus'oil (crude talloilacids) was heated at 50 C. for 2hours with lbs. of maleic anhydride.

Aomrc CLOCKER Annuc'r Example G 282 lbs. of oleic acid was heated with98 lbs. maleic anhydride for two hours at 250 C.

AcInIc CLOCKER Annuo'r Example H 580 lbs. of sperm oil was substitutedfor the 880 lbs. of soyabean oil in Example B.

AcInIc CLOCKER Annncr Example I In Examples A to H, preceding, thevarious oils were replaced by an equivalent weight of fatty acids, forinstance, 880 lbs. of linseed oil was replaced by 842 lbs. of linseedoil fatty acids.

AcInIc CLOCKER Ammo-r Example J Product of the kind described inExamples A to H, preceding, were saponified with a slight excess ofcaustic potash and then acidified with a slight excess of 50% sulfuricacid so as to yield products substantially identical with thosedescribed in Example I, preceding.

Acmrc CLOCKER Annncr Example K The various glycerides previouslydescribed were replaced by an equivalent amount of esters derived from alow molal alcohol, for instance, the ester derived from methyl, ethyl,propyl, or butyl alcohols, or cyclic alcohols such as benzyl alcohols,cyclohexanols, etc. Such esters are obtained COMPOSITION or MATTERExample v1 The Clocker adduct was pr pared from lin oil-and maleicanhydride, as described in Example A. To 1175 lbs. of the adduct wasadded 900 lbs.

oftriethanolamine. Themixture was stirred and heated at a temperatureo'f'200" for 8 hours. The product "was a clear, viscous, Ted oil,soluble in dilute alkali, colloidally soluble in kerosene.

COMPOSITION or. MATTER Example 2 The Clocker adduct was prepared fromsoyabean oil and maleic anhydride, .as described in Example B. To 1075lbs. of the adduct was added 600 lbs. .of triethanolamine. The mixturewas stirred and heated to a temperature of 250 for ahours.

COMPOsITION or MATTER Example 3 To 50 lbs. of the Clocker adductprepared from lndusoil and maleic anhydride, .as described in Example1F, was added 450 lbs. of triethanolamine. The mixture was reacted as inExample '1 to yield a viscous oil, which was soluble in dilute .alkaliesand ammonia.

1 112 lbs. of the Clocker adduct, prepared as described in Example D,was substituted for the 1075 lbs. of soyabean-maleic adduct in Example2.

COMPOSITION or NIATTER Example 6 To 1140 lbs. of Clocker adduct,prepared from the free fatty acids, as in Example J, was added 450 lbs.of triethanolamine. The mixture was reacted as in Example 2.

COMPOSITION OF MATTER Example 7 530 ,lbs. of :ethyl diethanolamine wassubstituted tor the. 600 lbs. of triethanolamine in Example 2.

COMPOSITION OF MATTER Example 8 Heat-polymerized triethanolamine wassubstituted for the triethanolamine in Example 2.

"-I-he'polymerized triethanolamine was prepared by heatingtriethanolamine at 250-300 C. for 4 'hours in the presence of about 0.5%of its weight 6 of sodium carbonate. Water in the amount of about 12% ofthe original weight of the .triethanolamine was evolved and .condensedduring the reaction COMPOSITION or .MATTER Example 9 Triethanolamine,heat polymerized triethanolamine, and ethyldiethanolamine, employed asreactants in prior examples, are first reacted with an alkylene oxidesuch as ethylene oxide in the ratio of three moles of C2H4O for eachavailable hydroxyl radical. 'Such etherized aminoalcohols aresubstituted in place of the reactant, as employed, without beingsubjected to the oxyalkylation step.

COMPOSITION or MATTER Example 1-10 Propylene oxide is substituted .forethylene oxide in the prior example.

COMPosIT-ION or MATTER Example 11 The proportion of alk-ylene oxide perhydroxyl radical is doubled in the two prior examples.

Reference to such esterification reaction of the kind previouslydescribed, contemplates that it shall be carried to completion, orsubstantial completion, from the standpoint of the desired ester. Aswill be pointed out hereinafter, such ester may be essentially amonomer, a dimer, a trimer, or higher polymer. Completion of reaction,or substantial completion, does not means that all available hydroxylradicals need be eliminated by reaction with carboxyl radicals, if thelatter are in excess or vice versa. Completion of the reaction may onlyinvolve the formation of a single ester linkage, i..e., the reaction ofone carboxyl with one hydroxyl radical. In any event, the final productOf reaction is subresinous or balsam-like 'in character.

Attention is directed to the fact that in the hereto appended claimsreference to tertiary aminoalcohols is intended to includepolyaminoalcohols, in which ah the occurrences of nitrogen atoms aretertiary. Examples of such tertiary amlnoalcohols are: Polymerizedtriethanolamine, .tetracthanolethylenediamine, symmetricaldiethanoldiethylethylenediamine, completely oxyethylatedtetraethylenepentamine, and the like.

For other examples of suitable tertiary polyamino alcohols see Examples9, and 11 of U. S. Patent No. 2,306,329, dated December '22, 1942, to DeGroote et al. See also completely oxyalkylated polyamines, such as thosedescribed in Examples 1 to 4, page 4, upper right hand column of U. S.Patent No. 2,324,490, dated July 20, 1943, to De Groote -et a1.Attention is directed additionally to another type of tertiarymonoaminoaicohols, which are very suitable for use in preparing thepresent compositions. Such compounds are obtained by the oxyalkylation,particularly the oxyethylation, of certain aminohydroxy derivativesobtained from the low molal nitroparaffins. More specifically, referenceis made to such compounds as are obtained by the oxyet-hylation of2-amino-l-butanol, 2-amino2- methyl-l-propanol, 2-amino 2 methyl 1 ,3-propanediol, 2 amino- 2 -ethyl-l,3-propanediol, and tris(hydroxymethyl)aminomethane insuch a manner as to-replace bot-h amino hydrogen atomswith hydroxyethyl radicals. In these instances the hydroxymethyl groupis the obvious chemical equivalent of the hydroxyethyl group. Additionaloxyethylation will convert the hydroxymethyl group into a radical inwhich the terminal group is a, hydroxyethyl radical. Oxyethylation oftris(hydroxymethyl)-aminomethane results in the formation of a compoundin which there are present five hydroxyalkyl radicals. Polymerization ofthis last mentioned product in the manner described in respect totriethanolamine results in an equally desirable reactant.

Previous references were made to the fact that a carboxyl radical may bepermitted to remain as such, 1. e., in the unneutralized state, or maybe neutralized in any suitable manner by means of a base such as causticsoda or the like, or by means of an amine. Similarly, any residualhydroxyl radical may remain as such, or be reacted with a low molalmonocarboxy acid. Similarly, the hydrogen atom of residual or terminalhydroxyl radical may be replaced by a low molal alkyl radical.

In the broadest aspect then, the new composition of matter employed asthe demulsifler of my process, is an esterified adduct being a member ofthe class consisting of complete esters, acid esters and ester salts;said adduct being an acylic alpha-beta unsaturated acid having not overcarbon atoms combined at an intermediate point in the carbon atom chainof a non-conjugated, unsaturated, non-hydroxylated, fatty acid acylradical having at least 8 carbon atoms and not over 32 carbon atoms;said esterified adduct containing at least one occurrence of the radicalin which n represents the numerals 2 to 20, and R and T represent alkyl,alieyclic, alkanol or arylalkyl groups. The CnHzn radical, the alkylradical and alkanol radical may have the carbon atom chain interruptedat least once by oxygen.

Examination of the preceding paragraph indicates that actually the scopeis somewhat larger than this aspect. If one or both of the radicals Rand T contain a hydroxyl group, then the alcoholic hydrogen atom may bereplaced by a low molal acyl radical. Such acyl radicals includebenzoic, methyl benzoic, and hydrogenated derivatives, 1. e., alicyclicanalogs.

The present products, since they contain basic amino groups, may, in theinstances where the molecule contains unreacted carboxyl groups,constitute compounds of the so-called "zwitterion" type and may actuallybe innermolecular or intramolecular salts.

If desired, the amino groups of the present compounds may be neutralizedwith inorganic acids, such as hydrochloric acid, sulfuric acid,phosphoric acid, etc., or with low molecular weight organic acids, suchas acetic acid, butyric acid, glycolic acid, lactic acid, phthalic acid,or the like. The solubility properties and surface activity of thesereagents may be conveniently modified by such neutralization of theamino groups with selected acids.

A more narrow aspect and preferred aspect of the present invention isillustrated by examples where the hydroxyamine is polyfunctional. Theadduct is always polyfunctional, due to the presence of anhydrideradicals or ester radicals, insofar that either radical is in essence acombined or potentially available carboxyl radical. If a glyceride, forinstance, linseed oil, is reacted with 3 moles of maleic anhydride, 6potential carboxyl radicals are introduced into the molecule.Occasionally, more than 3 maleic anhydride radicals, and probably asmany as 6 maleic anhydride radicals, can be so introduced. In any event,there is always a large plurality of carboxyl or potential carboxylradicals present.

The tertiary alkanolamine, as previously described, may be consideredfor the sake of simplicity as just an ordinary alcohol, as far asesteriflcation is concerned. Stated another way, one may temporarilyignore the amine function, and thus, the reactant may be considered as amonohydric alcohol or polyhydric alcohol. In the following discussionthe term alcohol" will be understood to include tertiary hydroxyamines.

If an alcohol is indicated by the formula Y'(OH)n, where n indicates thenumber 1 or more, and if a polybasic acid body be indicated by theformula X'(COOH);, where 12. indicates the number 2 or more, then thereaction between a monohydric alcohol and a polybasic acid will resultin a compound which may be indicated by the following formula: YX(COOH)71', wherein 12. indicates the number 1 or more, and which is in realitya contraction of a more elaborate structural formula, in which X and Y'are joined by a carboxyl radical or residue. Assumingyhowever, as wouldbe true in the majority of cases, that the alcohol actually would be apolyhydric alcohol, and that the acid body is polybasic in nature, thenexamination reveals that the formula might result in a combination, inwhich there were neither residual carboxyl radicals, nor residualhydroxyl radicals, or might result in compounds in which there wereresidual hydroxyl radicals, and no residual carboxyl radicals, orcompounds where there might be residual carboxyl radicals and noresidual hydroxyl radicals; or there might be both. This is indicated bythe following:

in which q indicates a small hole number (one in the case of a monomer,and probably not over 20 and usually less than 10), and m and n indicatethe number 1 or more, and m" and n" indicate zero or a small ormoderately-sized whole number, such as zero, one or more, but in anyevent, probably a number not in excess of 40; for instance, as would beindicated by a molecule which involved 6 to 1 moles of a polyhydricalcohol. Naturally, each residual hydroxyl could combine with a dibasicadduct or with a similar compound, which is essentially a tribasic acid,if derived from an acid such, as maleic acid; and in such event, therewould be a large number of free or uncomb-ined carboxyl radicalspresent, and especially, if derived from a trimaleated glyceride.Actually, the preferable type of reagent would be more apt to includeless than 20, and in fact, less than 10 free hydroxyl radicals. It isnot necessary to remark that the residual carboxyl radicals can bepermitted to remain as such, or can be neutralized in any suitablemanner, such as conversion into salts, esters, amides, amino esters, orany other suitable form. Usually, such conversion into salt form wouldbe by means of sodium hydroxide, potassium hydroxide, calcium hydroxide,magnesium hydroxide, ammonium hyamylamine, butanolamine,

droxide, ethanolamine, diethanolamine, triet-hanolamine,cyclohexanolamine, benzylamlne, aniline, toluidine, etc. Conversion intothe ester would be by means of a monohydric or polyhydric alcohol, suchas methyl alcohol, ethyl alcohol, propyl. alcohol. butyl alcohol, hexylalcohol, octyl alcohol, decyl alcohol; ethylene glycol, diethyleneglycol; glycerol, diglycerol, triethylene glycol, or the like. One couldemploy an amino alcohol so as to produce an ester.

If a tricarboxy acid, such as a maleic anhydride adduct, is employed,then at least theoretically three moles of the alcohol might react, withone mole of the acid compound. Similarly, as has already been pointedout, a large number of molecules of such polybasic acid adduct mightcombine with. a single molecule of a highly hydroxylated reactant. Forpractical purposes, however, we have. found that the most desirableproducts are obtained by combinations, in which the ratio of alcoholicbody to. the polybasic acid is within the. ratio of 3 to 1 and 1 to 5,and in which the molecular weight of the resultant product; does notexced 10,000, and is usually less than 5,000,, or perhaps less than3,000. This is particularly true, if the resultant product is soluble toa fairly definite extent, for instance, at least in some solvent, suchas water, alcohol, benzene, dichlorethyl ether, acetone, cresylic acid;or the, like. This is simply another way of stating that. it ispreferable, if' the product be one of the sub-resins, which are commonlyreferred to as an A resin, or B resin, as distinguished from a C resin,which is a highly infusible, insoluble resin (see Ellis, Chemistry ofSynthetic Resins, 1935, pa e 862, et seq.)

In recapitulating what has been said previously, the sub-resinous,semi-resinous, or resinous product herein contemplated as the preferredtype may be indicated by the following formula:

(COOH),,."

in which the characters have their previous significance, and representsa small whole number not greater than 5, and .r' represents a smallwhole number not greater than 5; Z represents a hydrogen ion equivalent,such as a metallic atom, organic radical, etc.

When used as demulsifiers for petroleum emulsions, the products ormaterials herein described, may be employed as such, or in admixturewith other demulsifiers, etc.

It is well known that conventional demulsifying agents may be used in awater-soluble form,

or in an oil-soluble form, or in a form exhibiting both oil and watersolubility. Sometimes they may be used in a form which exhibitsrelatively limited oil solubility. However, since such reagents aresometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to30,000, such an apparent insolubility in oil and water is notsignificant, because said reagents undoubtedly have solubility withinthe concentration employed. This same fact is true in regard to thematerial or compounds employed as the demulsifying agent of my process.

I desire to point out that the superiority of the reagent or demulsifyinagent contemplated in my process is based upon its ability to treatcertain emulsions more advantageously and at a somewhat lower cost thanis possible with other available demulsifiers or conventional mixturesthereof. It is believed that the particular demulsifylng agent ortreating agent herein descrl will find comparatively limitedapplication, so as the majority of oil field emulsions are c corned; butI have found that such a demuls ing agent has commercial value, as itwill e nomically break or resolve oil field emulsion: a number of caseswhich cannot be treated easily or at so low a cost with the demulsif;agents heretofore available.

In practising my process, a treating agenl demulsifying agent of thekind above descri is brought into contact with or caused to act u; theemulsion to be treated in any of the vari ways, or by any of the variousapparatus 1 generally used to resolve or break petrole emulsions with achemical reagent, the al: procedure being used either alone, or in combition with other demulsifying procedure, sue}: the electrical dehydrationprocess.

The demulsifier herein contemplated may employed in connection with whatis commc known as down-the-hole procedure, i. e., bri ing thedemulsifier in contact with the fluid: the well at the bottom of thewell, or at S( point prior to their emergence. This partici type ofapplication is decidedly feasible when demulsifier is used in connectionwith acidifi tion of calcareous oil-bearing strata, especi: if suspendedin or dissolved in the acid emplo for acidification.

It should be pointed out that acids and an' drides are chemicallyequivalent, and that 1 reference herein or in the claims to one or otheris meant to include both the acid and corresponding anhydride.

In some of the above examples, adducts maleic anhydride with sperm oilhave been 6 ployed. Chemical evidence indicates that reaction of maleicanhydride with esters of i saturated, long chain alcohols, such as speoil, involves the addition of maleic anhydride the chain or the alcoholin a manner analog to the addition of maleic anhydride to the ch ofunsaturated, non-conjugated, non-hydr ylated fatty acids. Interestingdemulslfiers r be prepared from the adducts of unsatura alcohols, suchas oleyl acetate, oleyl stear: jojoba nut oil, alcohol esters, and thelike, vi maleic anhydride or other alpha-beta ethyle acids or anhydridescontaining less than 10 car atoms. These products are prepared by the semanufacturing methods described herein for present compounds and haveutility in the se arts and process as the derivatives of the saturatedfatty acid adducts of the present plication. However, this applicationis not tended to cover compositions prepared from s adducts. Attentionis directed to the co-pen application of Charles M. Blair, Jr., and DaleSchulz, Serial No. 513,785 filed December 10, 1!

Demulsification, as contemplated in the he: appended claims, includesthe preventive ste; commingling the demulsifier with an aque component,which would or might subsequei become either phase of the emulsion, inabse of such precautionary measure.

Reference is made to my divisional applicai Serial No. 547,817, filedAugust 2, 1944, whei the materials used as the demulsifier of my he]described process, are claimed as new comp tions of matter.

Having thus described my invention, wha claim as new and desire tosecure by Let1 Patent is: 1. A process for resolving petroleum emulsi inwhich n represents the numeral 2 to 20, R and T are selected from theclass consisting of alkyl, alicyclic, alkanol and arylalkyl radicals,and Z is a member of the class consisting of hydrogen atoms and acylradicals having not over 8 carbon atoms.

2. A process for resolving petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsio to the action of a demulsifier,comprising a sub-resinous esteriflcation product of the formula type:

in which 11' represents a whole number not greater than 5, and :t'represents a whole number not greater than 5, and n, m, m indicate thenumeral to 40; q indicates a small whole number not over 20; Z is ahydrogen ion equivalent; Y is an ester radical derived from an aminoalcohol containing at least one occurrence of the radical in which nrepresents the numeral 2 to 20; R and 'I are selected from the classconsisting of alkyL.

alicyclic, alkanol and arylalkyl radicals, and Z is a member of theclass consisting of hydrogen atoms, and acyl radicals having not over 8carbon atoms; and X is a carboxylic adduct radical; said adduct being anacyclic alpha-beta unsaturated acid having not over 10 carbon atomscombined at one intermediate point in the carbon atom chain of anon-conjugated, unsaturated, non-hydroxylated, fatty acid acyl radicalhaving at least 8 carbon atoms and not over 32 carbon atoms.

3. The process of claim 1, wherein n is th numeral 2.

4. The process of claim 2, wherein n is the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid.

5. The process of claim 2, wherein n is the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid having not over 6carbon atoms.

6. The process of claim 2, wherein n is the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid having not over 6carbon atoms and in which Z is a hydrogen atom.

'I. The process of claim 2, wherein n is' the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid having not over 6carbon atoms and in which Z is a hydrogen atom and the fatty acylradical has 18 carbon atoms.

8. The process of claim 2, wherein n is the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid having not over 6carbon atoms and in which Z is an hi" drogen atom and the fatty acidacyl radical is a linoleyl radical.

9. The process of claim 2, wherein n is the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid having not over 6carbon atoms and in which Z is an hydrogen atom and the fatty acid acylradical is a linolenyl radical.

10. The process of claim 2, wherein n is the numeral 2, and the adductbeing that of a polybasic alpha-beta unsaturated acid having not over 6carbon atoms and in which Z is a hydrogen atom and the fatty acid acylradical is an oleyl radical.

CHARLES M. BLAIR. JR.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,262,358 De Groote et al Nov.11, 1941 2,325,062 Kritchevsky July 27, 1943 2,188,888 Clocker June 30,1940- 2,214,784 Wayne Sept. 17, 1940 2,306,281 Rust Dec. 22, 19422,312,731 Salathiel Mar. 2, 1943 2,319,034 Wayne, II May 4, 1943

